Molding compositions with solid thermoplastic elastomer thickeners and products obtained therefrom

ABSTRACT

A method of preparing thickened compositions which can be molded under low pressures and temperatures to provide thermoset articles, wherein liquid reactive components are slowly absorbed in solid thermoplastic elastomer thickeners such as thermoplastic ionomers and acrylic block copolymers. The thickener delays the viscosity build, allowing fiber reinforcement and other fillers to be incorporated, if desired, before molding. The molding composition is well suited for use in dentistry and other fields where small amounts or molding composition are used occasionally.

This application claims the benefit of the filing date of U.S.Provisional Application Ser. No. 60/391,925 filed Jun. 28, 2002.

FIELD OF THE INVENTION

This invention relates to the preparation of thermosetting moldingcompositions using a solid thermoplastic elastomer thickener withsecondary bonding.

SUMMARY OF THE INVENTION

The chemical and physical structure of the thermoplastic elastomerthickener is a tool for modifying and controlling the thickeningprocess, the blending of ingredients into a thermosetting moldingcomposition and the properties of the fully cured organic polymercomposition. The chemical and physical nature of the thermosettingmolding composition permits fiber reinforcement and other additives tobe easily incorporated therein.

These thermosetting molding compositions can be dispensed as premixeddoughs (bulk molding compounds), thick molding compounds or sheets(sheet molding compounds) and can be molded using low shear pressuremolding techniques and conditions of temperature and pressure to formarticles ranging from automotive parts to dental appliances to bathroomshower stalls. These solid thermoplastic elastomer thickeners allow foran extended shelf life in the uncured doughs.

The solid thermoplastic elastomer thickeners employed herein share thecommon feature of having reversible cross-links between polymer chains.This cross linkage is secondary bonding. Ionic bonds link segments ofpolymer chains in ionomers. Hydrogen bonds, Van der Waals forces,physical chain entanglement and crystal lattice interaction can alsolink segments of the polymer backbone of acrylic block copolymers. Theeffects of secondary bonding on plastic properties are similar tocovalent cross-linking but not to the same extent. For example,secondary bonding generally increases the melting temperature anddecreases the solubility. In addition, secondary bonding usuallyincreases the stiffness, strength and creep resistance of a plastic.

The suitable solid thermoplastic elastomer thickeners includethermoplastic ionomers such as “acrylic” containing ionomers, and,“acrylic” containing block copolymers. Particle sizes may be as small asa few microns (2 microns). The preferred particle size for the solidthermoplastic elastomer thickeners is determined by the delayedsolubility of the solid thermoplastic elastomer thickener in the liquidof the composition. These solid thermoplastic elastomer thickeners mayfunction effectively in concentrations as low as one (1) percent. Theeffective concentration of the solid thermoplastic elastomer thickeneris determined by the resin demand of the other solid ingredients in themix. The solid thermoplastic elastomer thickener is co-soluble in theliquid(s) of the composition whether these liquids are curable or not.For example, a some common solvent like acetone may be removed(evaporated) to convert the wet composition to a moldable dough. Theobjective is to maintain some time delay between the mixing of the solidand liquid ingredients of the molding composite and the initiation ofthe thickening process. Optional ingredients include long fiberreinforcement and additional thickeners such as alkaline earth oxidesand/or hydroxides.

Acrylic resins are well known and include polymer and copolymerformulations whose major monomeric components belong to two families ofesters: acrylates and methacrylates. The use of these polymers to formcomposite matrices is described in the following patents issued toRobert Guzauskas the inventor herein, U.S. Pat. Nos. 5,747,533,6,103,779 and 6,433,037. These patents are assigned to the same assigneeas the present invention. This invention takes that concept further tosolid thermoplastic elastomer thickeners with secondary bonding. Thesolid thermoplastic elastomer thickeners described herein offeradditional control of the properties and compatibilities of the moldingcompositions.

Two general classes of solid thermoplastic elastomer thickeners withsecondary bonding are thermoplastic ionomers and acrylic blockcopolymers. Preferred ionomers incorporate acrylic moieties.

In general the properties of the linear, random and alternatingcopolymers described in U.S. Pat. Nos. 5,747,553, 6,103,779 and6,433,037 are averages of the properties of the two or morehomopolymers. With block copolymers, the properties are not averages buta distinct property profile.

An ionomer has covalent bonds within the polymer chain and ionic bondsbetween the chains (Harcourt Dictionary of Science and Technology).Dupont copolymerized ethylene and acrylics in the 1960's to produceion-containing polymers. The product was named, “SURLYN”, and the newion containing copolymers were referred to as, “Ionomers”. Ionomers arenow made and sold by Dupont, A. Schulman, Network Polymers and Exxon.Commercially available ionomers include IOTEK®, ACLYN®, HIMIRA®,COATTHYLENE® and ESCOR®.

Acrylic resins comprise a majority of both the ionomers and blockcopolymers that can be used as solid thermoplastic elastomer thickenersof this invention. Polyvinyl polymers such as polyvinyl acetate andpolyvinyl alcohol are similar to acrylics with substitutions about theunsaturated bond linking two carbon atoms. These polymers can also beionomers and when the terms “acrylic” block polymer or “acrylic”containing block copolymers are used herein, they include such polyvinylpolymers.

In the book “Introduction to Ionomers”, Eisenberg and Kim defineionomers as polymers whose bulk properties are governed by ionicinteractions in discrete regions of the material. They add that ionomersare defined by properties rather than by composition, and, that thecrucial component of ionomers is the presence of electrically chargedionic groups along a polymer backbone. Ionomers have the common featureof containing ions (electrical charge centers) and neutralizingcounter-ions. Ionomers are differentiated from polyelectrolytes only bydegree. Polyelectrolytes are often quickly soluble in liquids. Ionomers(and block copolymers) are much less soluble. Ionomers generally, butnot always, have ion contents below 15 to 20 mol percent. Whereaspolyelectrolytes might have as many as one charged ion per “mer” unit.Typical ionomers are built upon hydrophobic, organic polymer backbones.Charged pendant groups are usually attached to the backbone. When ionsare located within the polymer backbone that arrangement is sometimescalled an ionene.

In the book, “Ionomers” the editors Tant, Mauritz & Wilkes, and authorsRobert Jerome and Mieczyslaw Mazurek argue that there are just two kindsof polymers: Ionic polymers that already contain charged groups; and,lonogenic polymers that are capable of receiving ionic groups. Theseionic groups may be randomly, or, regularly distributed along thepolymer backbone. This distribution creates a polyanion (negativelycharged), polycation (positively charged) or polyampholyte (neutralcharge). The backbone of the ionomers used in this invention ispreferably an acrylic polymer, or copolymer, or block polymer. Thesecharges are neutralized in whole or in part by counter ions. Anionomersare the most commercially important. Polyampholytes (Zwitterionomers)include many of the urethanes. Cationomers are generally the leastimportant group of ionomers.

The chemical structure of the solid thermoplastic elastomer thickenerdetermines it's morphology and together, chemical structure, polymermorphology and counterions determine the physical properties of thesolid thermoplastic elastomer thickeners. Some of the physicalproperties include solubility, glass transition temperature,crystallinity, plasticity, miscibility and the ability to blend intoother ingredients (compatibilization). Monochelic, telechelic and blockcopolymer structures are simply variants on the ionomer theme and havebeen produced with free radical polymerization or ionic polymerizations.

Many common ionomers have acrylic copolymer back bones such as thoselinear, acrylic polymers described in U.S. Pat. Nos. 5,747,553,6,103,779 and 6,433,037. This invention is a modification of the linearsolid acrylic compositions and the methodology described in U.S. Pat.Nos. 5,747,553, 6,103,779 and 6,433,037. The acrylic thickenersdescribed in U.S. pat. Nos. 5,747,553, 6,103,779 and 6,433,037 can beformed into ionomers. The acrylic polymers described therein are,“monochelic” ionomer structures, i.e., there is a single ion at one endof the polymer. The term “ionomer” as used herein, refers to polymershaving more than a single ion. Additional versatility is provided byvariations of this “monochelic ionomer” structure in providingthickeners. An otherwise linear, solid “monochelic”, ionomer backbonemay be decorated along it's length with positively or negatively chargedgroups, or combinations thereof. Examples of anions are carboxylates,sulfonates, and phosphonates. The charged group associates with acounter ion such as Na+, Li+, Mg++, or Zn++ in the case of anions.Cationic polymers are also quite common in the ionomer literature.Pendant pyridine groups are the most common examples. Other cationsinclude aliphatic or aromatic amines. Sulfonium and phosphonium ionshave also been incorporated into polymeric systems as have ammonium andpyridinium. Many counter ions can be used with these charged polymers.

In addition to changing the charge associations with the ionomer, all ofthe usual techniques of polymer science can be used to modify and thuscontrol the physical and chemical properties of these ionomers.

The mechanism of delayed solubility, essential to the thickening actionof the otherwise linear polymer thickener, is altered by the chemicaland physical nature of ionomers. This delayed solubility is altered bythe structure of the polymer backbone, which may be linear or branched,and by the choice and the concentration of the neutralizing counterions. These alterations are most probably due to changes in molecularmorphology: the coiling of the polymer backbone and the aggregation andinteraction of ionic domains. Glass transitions can illustrate thepresence of secondary bonding forces of sufficient magnitude to alterthe physical properties of an organic polymer, such as delayedsolubility.

Acrylic ionomers are well known and are commercially available. Thesynthesis of such ionomers relies upon two general methods:

-   1) Polymerization of monomers with ionic groups, and-   2) Chemical modification of susceptible (ionogenic) polymers.

The resulting ionomers may have randomly distributed ionic groups, or,regularly distributed ionic groups. Random ionomers may contain anions(anionomers), cations (cationomers) or both anions and cations(polyampholytes and Zwitterionomers). Free-radical polymerizations aretypically initiated by azo compounds or peroxides. Iononic routes canalso be used. Random anionomers commonly contain carboxylate, sulfonateor phosphonate groups that are typically neutralized with alkali, alkaliearth, transition metals or organic cations. The major cationomerscontain ammonium, sulphonium or phosphonium. Their counterions mayinclude halides and organic anions.

That acrylic monomers can be polymerized in liquid suspensions usingfree radical initiators such as AIBN is well known. Such polymers haveminimal molecular cross-linking, are thermoplastic and are more or lesssoluble in various low molecular weight liquids. Since thesethermoplastic polymers are easily molded using injection-moldingoperations, they are available from commercial manufacturers. But linearthermoplastic polymers easily absorb surrounding liquids, includingwater, with resultant swelling and sometimes dissolution. So whereabsorbed liquids or thermoplasticity may be a problem, cross-linked,thermoset, acrylic polymers are preferable. Thermosetting resins are theplastic of choice in many industries since the cross-linked polymersresist penetration by many liquids and resist distortion by heat ormechanical stress. Ionomers have the general characteristics ofthermoplastics but have an ionic cross-linking of the polymer back boneacross the charged pendant groups.

Methyl-methacrylate, ethylacrylate and acrylic acid are common acrylicmonomers. Acrylic monomers can polymerize by a free radical, additionreaction. Two commercially used initiators for free-radicalpolymerization of acrylics are the peroxide initiator: benzoyl peroxide(BPO) and the aliphatic azonitrile initiator: azobisisobutyronitrile(AIBN). Both BPO and AIBN will decompose into free-radical activators atambient temperature.

Peroxide initiated polymerizations tend to be more vigorous which caninduce polymer chain decomposition with subsequent cross-linking betweenchain fragments. Cross-linking produces three dimensional networkpolymers that are said to be thermoset. AIBN and other azonitrileinitiators produce lower polymerization exotherms, little polymer chaindecomposition, minimal cross linking and linear, thermoplastic acrylicresins. In addition, azo initiators irreversibly decompose when heated.Therefore, residual azo initiator, AIBN, can be eliminated from acrylicresin by the deliberate heating of the resin. The resulting, essentiallylinear polymers, with the very narrow molecular weight distribution arethose preferred for ionomers. The thermoplastic polymer can be convertedto an ionomer by melting and mixing in a suitable salt such as sodium orlithium carbonate, magnesium hydroxide or zinc oxide. Other direct andindirect syntheses are available.

The deliberate cross linking of the secondary bonding found in ionomersand block copolymers used herein provides delayed solubility, i.e.,delayed thickening, so it may prove practical to reduce the size of thesolid polymer beads to a finer powder, and, to reduce the molecularweight of the polymer backbone to facilitate solubility, miscibility andother physical and chemical properties as desired by a compounderskilled in the art.

There is a distinction between using alkaline earth materials asthickeners in chemically thickenable resins to produce a moldable dough(typically a Sheet Molding Compound), as opposed to the use of alkalineearth materials as simple fillers in resins which cannot be chemicallythicken. The thermoplastic elastomer thickeners of this inventionthickened by a physical process and can thicken resins which do notchemically thicken. The presence of CaO, Ca(OH), MgO, or Mg(OH) in thecompositions with resins which do not chemically thicken function assimple fillers. Calcium carbonates, limestone and gypsum are someexamples of compositions which can be simply fillers.

Although the acrylic doughs provide useful molded articles, the physicalproperties are not ideal for all applications and have been manipulatedby blending methyl methacrylate with other resins, forming copolymerswith the methyl methacrylate monomer and/or increasing the degree ofcross-linking between polymer chains. Adding fiber reinforcement isdesirable for some applications.

Long fibrous fillers, such as glass, carbon, aramid, etc., are known togreatly enhance strength, stiffness and toughness of plastic materials.Long fibers being defined as lengths equal to or exceeding the criticalaspect ratio of the fiber matrix combination. Plastics reinforced withsuch long fibrous inclusions, i.e., composites, exhibit physical andchemical properties that are a composite of the properties of thefibrous fillers and plastic matrix. Typically, the included fiber hastensile strength much higher than the resin matrix, is insoluble in theresin matrix and is chemically, or physically bonded to the resin matrixin such a way as to deflect a crack propagating through the resin matrixalong the length of the fiber-matrix interface. Fibers turn the crack,absorb the energy of fracture, reduce the incidence ofthrough-and-through-fracture, and give composites their characteristicproperties of high strength, high stiffness, toughness and lightweight.The properties of some conventional polymeric materials and compositesare disclosed in CRC Practical Handbook of Materials Science, Ed.Charles T. Lynch, 1994, pp. 547–548 (vinyls, ASA resins), 327–328 (glassfiber, organic fiber) and 342 (organic matrix composites). While the useof long fibrous fillers can provide advantageous physical properties,fiber is difficult to incorporate into a resin matrix, particularlywhere the matrix resin is highly viscous.

Conventional thermosetting acrylic thickened doughs of powdered, lowmolecular weight acrylic resin and lightly inhibited acrylic monomerliquid are highly viscous. The mixture quickly passes from a wet slurry,to a viscous paste and then to a moldable dough as the resin particlesfirst absorb and then dissolve in the monomer. Unfortunately, thisotherwise convenient, rapid transition from slurry to paste to doughproduces a very abrupt rise in viscosity. In addition, residual BPOinitiator in the acrylic resin powder, intended to thermoset the mix,begins spontaneous decomposition, initiates polymerization and canreduce the shelf life of the fresh dough to only a few hours at 80° F.

Early efforts to bring a thermoset, fiber reinforced, organic polymercomposite to the dental market have floundered on the two problems of 1)prematurely high viscosity; and 2) premature gelation (polymerization).Viscosity is intentionally built-up rapidly in dental acrylic as finelypowdered, low molecular weight resins are dissolved in monomer to makemoldable dough. Premature gelation is a consequence of the demand forlow curing temperature. Adding reinforcing fibers to this increasinglyviscous mix quickly becomes impractical. Adding long fibers to anyliquid causes the liquid to become intractably thick, even at levels ofonly 2 wt. %. As disclosed by J. E. Gordon in The New Science of StrongMaterials, 2nd Ed., p. 177, Princeton Univ. Press, “Beyond two percent,therefore, it is impossible to add fibers to a matrix and it becomesnecessary to add the matrix to the fibers.” Prolonged mixing withsignificant energy input and subsequent heat build up is required toincorporate fibers into liquid monomer and wet the fiber reinforcement.

Dental researchers have long wrestled with the problem of incorporatingreinforcing fibers into thermoset, molding doughs. For example,Ladizesky, Chow and Cheng, using a cloth, impregnated with acrylicsyrup, disclose, “The added technical procedure to construct the (fiber)reinforced dentures required an additional two hours (20%) of thestandard laboratory time.” Denture Base Reinforcement Using WovenPolyethylene Fiber, International Journal of Prosthodontics, Vol. 7, No.4, p. 307–314 (1994). Targis® by Ivoclar is an example of a commercialpre-preg used in dentistry.

In the 1960's, Bowen, U.S. Pat. No. 3,066,112 incorporated particulateglass fillers into acrylic and vinyl ester resins used as dentalfillings. Since then, small particulate fillers have been used to reducethe shrinkage of polymerization, increase hardness and improve abrasionresistance of these dental materials. However, these particle filledmaterials do not behave as fiber reinforced composites. Unless thecritical aspect ratio, length/diameter, of a reinforcing fiber embeddedin a resin matrix is equaled or exceeded, the composite material failsat low stress levels. Early dental composites did not containparticulate fillers with aspect ratios exceeding 4/1. In dentalpractice, particulate fillers are nearly spherical to enhance flow andmixing. Consequently, there is very little resistance to crackpropagation in these composites. The result is very little enhancementin strength, stiffness and toughness of the dental composite material.Short particle fillers can actually make the dental materials brittle.

Fiber reinforcement has been incorporated in thermosetting moldingdoughs on an industrial scale and fiber reinforced industrial moldingdoughs are available as bulk molding compound (BMC) or sheet moldingcompound (SMC). However, these compounds have extremely high viscositiesof 20–30 million centipoise. These high viscosities are manageable onthe industrial scale where large hydraulic or electric presses can beused to generate the high molding pressures and temperatures necessaryto mold these compounds. It is desirable to reduce these pressure andtemperature requirements to enable molding of fiber reinforced resinsunder low pressure molding conditions.

Short shelf life, high molding pressure and temperature requirementshave prevented the commercial production and distribution of fiberreinforced, polyester/acrylic, vinyl ester and acrylic, molding doughsto the very small user doing an occasional or opportunistic molding.Perishable, industrial BMC and SMC has, until now, been unsuitable forthe small batches of premix used on the occasional, very small job ofthe dentist, the auto body mechanic, the boat repair person or the like.The small of occasional user, like the dentist, requires a doughmoldable with manual pressure, curable at hot water temperatures andwith a long shelf life at ambient temperature for their opportunistictype of work.

The use of additives to reduce the viscosity of the molding dough forlow-pressure molding has had limited success. See: Proceedings,Composites Institute 51st Annual Conference and Expo 96.

Factors which prevent the easy, on site mixing of resin powders andreinforcing fibers, with curable liquid monomers include:

-   1) Resin particles and fibers tend to separate into layers and    clumps, called agglomeration, and require periodic stirring to    prevent this separation.-   2) Prolonged mixing is required to incorporate particles and fibers    into liquid monomer and thoroughly wet the particulate fillers and    fiber reinforcement. If the resin particles dissolve immediately,    viscosity build up prevents further mixing.-   3) Dry ingredients must be very dry. Water contaminated powder and    fiber will contaminate and weaken the composite. Surface moisture,    adsorbed at ambient temperature, must be removed from particles and    fibers so the monomer can wet and bond to these ingredients.    Interfacial bonding between solid fillers and curable liquids must    occur during polymerization if physical properties are to be    enhanced rather than degraded in the composite.-   4) The need for special processing equipment so that air is not    incorporated in the mix producing porosity in the finished product.

Drying and mixing require time and special equipment not available tothe opportunistic molder working at the occasional job.

The present invention provides fiber reinforced thermosetting bulkmolding compounds (BMC), thick molding compounds (TMC) and sheet moldingcompounds (SMC) and precursors thereto with extended shelf stability.

The present invention also provides a solid thermoplastic elastomerthickener with secondary bonding for thermosetting molding compositions(BMC, TMC, SMC) which delays viscosity build-up to provide anopportunity to incorporate long fiber reinforcement and/or otheradditives and employ low pressure molding techniques without heating.

The present invention also provides a solid thermoplastic elastomerthickener with secondary bonding for thermosetting molding compositionswhich thickens by a physical mechanism and not a chemical mechanism, andparticipates in the cure.

The present invention also provides a solid thermoplastic elastomerthickener having reversible cross-links between polymer chains.

The present invention also provides a solid thermoplastic elastomerthickener for thermosetting molding compositions which facilitates themiscibility of the ingredients of the thermosetting moldingcompositions.

The present invention also provides a solid thermoplastic elastomerthickened thermosetting molding compositions, precursors thereto andmethods for their preparation, which allow long fiber reinforcement tobe easily incorporated therein.

The present invention also provides fiber reinforced thermosetting bulkmolding compounds (BMC), thick molding compounds (TMC) and sheet moldingcompounds (SMC) and precursors thereto which can be molded under thepressures and temperatures of low pressure molding equipment.

The present invention provides an acrylic ionomer thickenedthermosetting composition suitable for fiber reinforced molded retailproducts.

The present invention also provides a thermosetting premixed acrylicionomer thickened molding composition, optionally with fiberreinforcement, suitable for dental appliances to reduce exposure ofoperator and patient to hazardous vapors.

The present invention also provides an ionomer thickened thermosettingmolding composition which has an extended shelf life so as to reducewaste and/or make the product available to retail customers.

The present invention also provides a thermoplastic elastomer thickenedthermosetting molding composition which experiences less shrinkage uponcure, requiring fewer adjustments (secondary finishing), to complete thepart.

The present invention also provides a thermoplastic elastomer thickenedthermosetting molding composition, optionally with long fiberreinforcement, which is compatible with existing techniques, equipmentand procedures for producing dental appliances.

These embodiments are provided through the methods and compositions ofthis invention which comprises molding compositions and precursorsthereto. This includes bulk molding compositions, thick moldingcompositions and sheet molding compositions. The BMC, TMC and SMC ofthis invention are each composed basically of four principleingredients: thermosetting resins (resin solution) optionally fibers,optionally fillers and optionally additives. Only the resin solution isrequired for this invention. With this overall combination in place, itis feasible to use various types of specific ingredients to meet therequired properties of the final product, and that makes BMC, TMC andSMC very versatile. Reinforced composites can be produced with an almostindefinite number of possible formulations.

Suitable resin solutions are made by dissolving a curable thermoplasticelastomer thickener in a curable monomer, oligomer or polymerco-solvent, as a means of making a curable molding composition. Theresin solution may contain other resins that are soluble in the monomeroligomer or polymer, e.g.:

-   a) acrylic resins dissolved in a polymerizable monomer co-solvent    where the polymerizable monomer co-solvent dissolves both the    acrylic resin and the solid thermoplastic elastomer thickener, with    styrene monomer, acrylic monomer, EGDMA (ethylene glycol    dimethacrylate), TEGDMA (triethylene glycol dimethacrylate), UEDMA    (urethane dimethacrylate) and similar acrylates being examples of    monomer co-solvents;-   b) polyester resins dissolved in a polymerizable monomer co-solvent,    where the polymerizable monomer co-solvent dissolves both the    polyester resin and the solid thermoplastic elastomer thickener,    with styrene monomer, acrylic monomer, EGDMA, TEGDMA, UEDMA and    similar acrylates being examples of monomer co-solvents;-   c) styrenic resins dissolved in a polymerizable monomer co-solvent,    where the polymerizable monomer co-solvent dissolves both the    styrenic resin and the thermoplastic elastomer thickener, with    styrene monomer, acrylic monomer, EGDMA, TEGDMA, UEDMA and similar    acrylates being examples of monomer co-solvents; and-   d) vinyl ester resins dissolved in a polymerizable monomer    co-solvent, where the polymerizable monomer co-solvent dissolves    both the vinyl ester resin and the solid thermoplastic elastomer    thickener, with styrene monomer, acrylic monomer, EGDMA, TEGDMA,    UEDMA and similar acrylates being examples of monomer co-solvents.

The addition of fiber(s) provides a means for strengthening orstiffening the polymerized resin solution. The types often used are:

-   1) inorganic crystals or polymers, e.g., fibrous glass, quartz    fibers, silica fibers, fibrous ceramics, e.g., alumina-silica    (refractory ceramic fibers); boron fibers, silicon carbide whiskers    or monofilament, metal oxide fibers, including alumina-boria-silica,    alumina-chromia-silica, zirconia-silica, and others;-   2) organic polymer fibers, e.g., fibrous carbon, fibrous graphite,    acetates, acrylics (including acrylonitriles), aliphatic polyamides    (e.g., nylons), aromatic polyamides, olefins (e.g., polypropylenes,    polyesters, UHMW polyethylenes), polyurethanes (e.g., spandex,    alpha-cellulose, cellulose, regenerated cellulose (e.g., rayon),    jutes, sisals, vinyl chlorides (e.g., nylon), vinyl chlorides (e.g.,    vinyon), vinyldienes (e.g., saran), flax and thermoplastic fibers;-   3) metal fibers, e.g., aluminum, boron, bronze, chromium, nickel,    stainless steel, titanium or their alloys; and-   4) “Whiskers”, single, inorganic crystals.

The reinforced fibers can be in the form of a woven fabric or mat, abraided fabric or mat, a knitted fabric or mat, a loose-laid fabric ormat, or a sewn fabric or mat.

Suitable nonfibrous filler(s) are inert, particulate additives beingessentially a means of reducing the cost of the final product whileoften reducing some physical properties of the polymerized, resin-fibercomposite include calcium carbonates of various forms and origins,silica of various forms and origins, silicates, silicon dioxides ofvarious forms and origins, clays of various forms and origins, feldspar,kaolin, flax, zirconia, calcium sulfates, micas, talcs, wood in variousforms, glass (milled, platelets, spheres, micro-balloons), plastics(milled, platelets, spheres, micro-balloons), recycled polymer compositeparticles, metals in various forms, metallic oxides or hydroxides(except those that alter shelf life or viscosity), metal hydrides ormetal hydrates, carbon particles or granules, alumina, tabular, aluminumpowder, aramid, bronze, carbon black, carbon fiber, cellulose, alphacellulose, coal (powdered), cotton, fibrous glass, graphite, jute,molybdenum, disulfide, nylon, orlon, rayon, silica, amorphous, sisalfibers, fluorocarbons and wood flour.

Suitable additives include polymerization initiators. Initiators are themeans of generating the free radicals that begin and sustainpolymerization. Said initiator-monomer combination, otherwise stable forat least a week at ambient temperature, is activated by means ofelevating temperature, or by exposing to microwave, infrared, visible,ultra-violet or shorter radiations thus generating free radicals.Specific initiators are described below

The solid thermoplastic elastomer thickener is used as the means ofthickening the polymerizable resin solution into a moldable dough. Thesesolid thermoplastic elastomer thickeners are typically ionomers such asacrylic ionomers or acrylic block copolymers in the form of solidpowders or beads. A general formula of typical sheet molding, thickmolding and bulk molding compounds, employing a variety of freeradicals, initiators and other ingredients, which can be used in themethod of thickening polymerizable resin solutions into moldablecompositions provided by this invention follows. The solidionomer/acrylic block copolymer powders or beads can be essentiallylinear or branched, acrylic polymers which act by slowly absorbing thepolymerizable monomer resin solvent. The solid acrylic ionomer/acrylicblock copolymer powder or bead thickeners are essentially free ofinitiators as a means to extend shelf life. These acrylic ionomer/blockcopolymer powder or bead thickeners are of a molecular weight, chemicalcomposition and diameter as a means to be both slowly dissolving in andhighly absorbing of the polymerizable monomer, oligomer or polymersolvent.

The following are functional additives and a means of impartingdesirable properties to the molding composition or to the curedcomposite. These include, but are not limited to, anti-blocking agents,anti-caking agents, anti-foaming agents, antioxidants, anti-slip agents,anti-static agents, blowing agents, coupling agents, compatibilizers,dispersing aids, flatting agents, inhibitors, catalysts,accelerators/promoters, heat stabilizers, light stabilizers, wettingagents, plasticizers, extenders, thixotropics, flame, fire and smokeretarders, internal mold releases, lubricants, impact modifiers,tougheners, coloring/dyes/pigments, odorants and deodorants, low profileor low shrink additives, low pressure additives, clarifying agents,opacifiers, thickeners, viscosity control agents, permeabilitymodifiers, solvents, waxes and thermoplastics.

The molding compositions preferably comprise:

-   a) a liquid monomer, oligomer, polymer or combination thereof,    containing vinyl unsaturation, which polymerizes in the presence of    an activated free-radical polymerization initiator and serves as a    co-solvent for the solid resins;-   b) at least one (1) wt. %, based on the total weight of liquid    monomer, oligomer, polymer or combination thereof containing vinyl    unsaturation in the composition, of a solid thermoplastic elastomer    thickener having secondary bonding, preferably an ionomer or acrylic    block copolymer thickener most preferably an acrylic ionomer    thickener, wherein the solid thermoplastic elastomer thickener is:-   i) soluble in said liquid monomer, liquid oligomer, liquid polymer    or combination thereof containing vinyl unsaturation,-   ii) reactive with the liquid monomer liquid oligomer, or liquid    polymer or combination thereof in the presence of an activated    free-radical polymerization initiator free of active free-radical    polymerization initiators, the acrylic ionomers/block copolymers    liquid monomer, oligomers, polymers;-   c) optionally, 0.5 wt. % or more, preferably 10 wt % or more based    on the total weight of the composition, of long fiber reinforcement    having an aspect ratio (L/D) greater than 5:1 and an average length    of at least 0.25 mm, which is insoluble in the liquid monomer,    oligomer, polymer or combination thereof;-   d) a free-radical polymerization initiator, the activity of which    can be restrained under ambient conditions or is inactive at ambient    temperature so as to provide a shelf life of at least one month at    ambient temperature.

The precursors to a molding composition comprise a thermosetting resinsolution of:

-   a) a curable liquid monomer, liquid oligomer, liquid polymer or    combination thereof containing vinyl unsaturation, which polymerizes    in the presence of an activated free-radical polymerization    initiator;-   b) about one (1) wt. %, of the total weight percent of the liquid    monomer, liquid oligomer, liquid polymer or combination thereof in    the composition, of a solid thermoplastic elastomer thickener,    preferably an acrylic ionomer or acrylic block/copolymer thickener    resin which is soluble in and reactive with said liquid monomer,    liquid oligomer, liquid polymer or combination thereof containing    vinyl unsaturation. At least a portion of said liquid monomer,    oligomer, polymer or combination thereof containing vinyl    unsaturation is absorbed in the thermoplastic elastomer thickener,    which is free of free-radical polymerization initiators; and-   c) optionally 0.5 wt. % and above preferably 10 wt % or more, based    on the total weight of the composition, of long fiber reinforcement    having an aspect ratio (L/D) greater than 5:1 and an average length    of at least 0.25 mm, which is insoluble in the liquid monomer,    liquid oligomer or liquid polymer.

The precursor compositions are shelf stable for at least one month andare preferably free of alkali earth metal oxide fillers and activefree-radical initiators.

The methods comprise:

-   a) mixing a solid thermoplastic elastomer thickeners having    secondary bonding such as an a thermoplastic ionomer or acrylic    block copolymer, which is free of active free-radical polymerization    initiators, with one or more liquid monomers, liquid oligomers,    liquid polymers or a combination thereof with vinyl unsaturation    which polymerizes in the presence of an activated free-radical    polymerization initiator, wherein said solid thermoplastic elastomer    thickener absorbs said liquid monomers, liquid oligomers, liquid    polymers or combination thereof, and reacts with said liquid    monomers, liquid oligomers, liquid polymers and combinations    thereof, absorbed therein, in the presence of an activated    free-radical polymerization initiator; and optionally-   b) aging the mixture of solid thermoplastic elastomer thickener    resin, liquid monomer, oligomer, polymer or combination thereof    containing vinyl unsaturation, and optional long fiber reinforcement    for at least 24 hours to allow absorption of the liquid monomer,    oligomer, polymer or combination thereof, by the solid acrylic    resin.

This invention involves the preparation of novel compositions of stable,thermosetting, acrylic, styrenic, vinyl ester or polyester thickeneddoughs. Preferred embodiments of these compositions can be compounded tobe compression molded at low pressure such as that from the manual screwor small hydraulic press familiar to a dental-laboratory or low pressuremolding equivalents. The preferred compositions can be cured at lowtemperatures using a hot water bath or UV or visible light sourcefamiliar to a dental laboratory. These compositions preferably include ahighly absorbent, solid acrylic ionomer or acrylic block copolymer resinwhich functions as a thickener and allows the economic, bulk manufactureand packaging of fiber reinforced polyester, vinyl ester, styrenic oracrylic thickened compositions. This same highly absorbent, solidacrylic ionomer/acrylic block copolymer thickener resin allows a laterdistribution of the small quantities of these molding compositions tousers remote in time and place from their site of manufacture.

The fiber reinforced acrylic, vinyl ester/acrylic and polyester/acrylichave a combination of sufficiently:

-   -   1) long shelf life;    -   2) low molding pressure; and    -   3) low curing temperature        to be practical for the dentist or, the low production volume,        custom molder, or the occasional molder at the opportunistic        job.

The solid thermoplastic elastomer thickener is preferably a, soluble,highly absorbent, high molecular weight and unbranched thermoplasticacrylic resin, although branched polymers can be used. This thickenerdefeats the problems of:

-   1) Rapid viscosity build up during mixing of ingredients which    prevents the thorough mixing and wetting of fillers and fibers by    the liquid; and-   2) Premature dough gelation.

The slowly soluble solid thermoplastic elastomer thickener withreversible cross-links via secondary bonding allows prolonged mixing offiber, filler and liquid ingredients for periods as long as one hour.The slow dissolution of the solid thermoplastic elastomer thickenerresin delays viscosity build up for a length of time required tothoroughly mix and wet reinforcing fibers in the premix slurry. Thisunique solid thermoplastic elastomer thickener resin can act entirelywithout alkaline earth additives. During a period of maturation,typically 1–4 days, the solid thermoplastic elastomer thickener absorbsthe monomer solvent and dissolves to form a curable dough. This periodof maturation allows the thermoplastic elastomer thickener to convertthe wet slurry first into a paste and then into a dough. This dough canremain moldable at a low pressure for many months and as long as twoyears when totally devoid of unstable initiators of polymerization suchas benzoyl peroxide or azo initiators in the case of acrylic ionomers oracrylic block copolymers. Since the solid acrylic acrylic ionomer orblock copolymer thickener is preferably devoid of active initiators,stable initiators such as t-butyl peroxybenzoate and inhibitors can beincorporated into the molding compositions to avoid premature gelationof the dough. This facilitates a long shelf life.

The preferred acrylic resin used to form ionomer thickeners is anunbranched polymethyl methacrylate resin (PMMA) polymerized with an azoinitiator in a suspension polymerization to a molecular weight of about400,000 as determined by GPC using a conventional solvent for PMMAresins in about 0.1 mm particles/beads. An amount of 0.25 grams of a400,000 molecular weight polymer dissolved in 50 ml of methylenechloride measured at 20° C. using a No. 50 Cannon-Fenske viscometer hasan inherent viscosity of 1.25. These resins are commercially availablefrom ICI Chemical under the trade name Elvacite® 2051. The ionomer canbe created by melting this thermoplastic polymer and mixing in aninorganic salt.

This preferred thickening agent, a thermoplastic, solid acrylic ionomerthickener resin, is created by raising the temperature of the resinabove the decomposition temperature of the azo initiators to eliminateresidual initiator. This can be done in the autoclave immediatelyfollowing suspension polymerization. Or, the resin particles/beads canbe baked at up to 100° C. Either method decomposes and eliminatesresidual azo initiator. Baking may cause the particles/beads to sticktogether in aggregates. The baked particle/bead aggregate can be tumbledin a drum mixer for 30 minutes to break up clumps of resin beads.Preferably the polymer is baked at a temperature above the decompositiontemperature of the azo initiator but below the polymer's glasstransition temperature to avoid resin fusion.

A large particle/bead size minimizes the soluble exposed surface areaand a very large high molecular weight minimizes polymer solubility.Various combinations of bead size and molecular weight make the beadsmore or less soluble during compounding. It's relative insolubilityallows the resin to mix with a liquid monomer, oligomer or polymer,preferably methyl methacrylate, without producing a noticeable immediateincrease in viscosity. The preferred thickening agent slowly absorbs theliquid, swells and dissolves during a one to four day maturation periodin a sealed container at 70° F. The incubator is inverted at least onceevery 24 hours. During this maturation period, the viscosity of the wetslurry increases to a paste and then plateaus at a doughy consistencyhaving more or less tack and viscosity depending on the nature and theratios of liquid to solid ingredients.

With long fiber reinforcement incorporated therein, the moldingcomposition provides thermoset articles, including dental appliances,which are composites with a unique property profile. These compositescan substitute the metal frameworks and superstructure used to supportdental crowns and bridgework. These composites also provide analternative to ceramic build-ups and appliances made by lost waxcasting. In addition to enhancing physical properties, the fiberreinforcement reduces shrinkage in the molded article, requiring feweradjustments and finishing steps.

The relatively long shelf-life of the molding compositions of thepresent invention of at least one week provides adequate time touniformly blend in the fiber reinforcement, even where mixing forextended periods of over one hour is required. Where the shelf lifeextends beyond one year, premixes can be prepared and waste is reduced.The extended shelf life is determined by the initiator and the additivesutilized. Preferably, benzoyl peroxide catalyst is avoided, unless itsactivity at ambient temperature is suppressed, and the use of alkalimetal oxide fillers to thicken the formulation is avoided.

Acrylic resins form a major component of the thickener and moldingcompounds of this invention. The term “acrylic resins” as used herein isintended to include acrylic monomers of the structure:

wherein R=H or a hydrocarbon based radical, and

-   -   R¹=a hydrocarbon based radical; and oligomers, polymers and        copolymers thereof. Included within the acrylic polymers are        linear, branched and cross-linked homopolymers. Included within        the acrylic copolymers are graft copolymers, random copolymers,        block copolymers and cross-linked copolymers with two or more        acrylate monomers of formula I or different monomers such as        styrene and acrylonitrile (ASA resins) and acrylamide and        methacrylamide. The preferred acrylic resins are the monomers,        polymers and copolymers, both linear and cross-linked, of        methylmethacrylate and ethylmethacrylate.

The hydrocarbon based radicals of R and R¹ include methyl, ethyl,propyl, isopropyl, and n-butyl, sec-butyl, isobutyl, tert-butyl, hexyl,heptyl, 2-heptyl, 2-ethylhexyl, 2-ethylbutyl, dodecyl, hexadecyl,2-ethoxyethyl isobornyl and cyclohexyl. Preferred acrylates have R andR¹ selected from the C₁–C₄ series. The most preferred acrylic polymer isbased on methylmethacrylate. A preferred methylmethacrylate acrylicpolymer is Elvacite® 2051, available from ICI.

As indicated above, the terms “acrylic” and “acrylic resin” as usedherein, are intended to include polyvinyl alcohols and polyvinylacetates such as those derived from Bis GMA. Bis GMA is essentially anoligomer of the formula

wherein R is

which can be obtained by reaction of one molecule of bisphenol-A and 2molecules of glycidylmethacrylate or by reaction of diglycidylether ofbisphenol-A with methacrylic acid. Similar vinyl esters can be preparedusing other polyepoxides and unsaturated monocarboxylic acids. Theseresins are cured at ambient or elevated temperatures by free-radicalpolymerization in a manner analogous to the acrylic resins containingmonomers of formula (I) above.

The terms “acrylic” and “acrylic resin”, as used herein, are alsointended to include polymers and copolymers of the acrylate monomersdescribed above and polymers produced from Bis-GMA described above.

The compositions of this invention include a liquid monomer, liquidoligomer or liquid polymer with vinyl unsaturation which cures to athermoset polymer in the presence of a free-radical polymerizationinitiator. The liquid monomer oligomer or polymer must also be able tosolubilize the solid thickener resin so that the liquid monomer,oligomer or polymer will be absorbed by the solid thickener resin.Suitable liquid monomers, oligomers and polymers include the liquidacrylic monomers described above and liquid oligomers (diacrylates anddimethacrylates) and polymers obtained therefrom. Suitable liquidoligomers and polymers also include the liquid Bis-GMA oligomers andpolymers described above and further include liquid polyester resins andliquid styrene monomers and oligomers. Examples of dimethacrylatesinclude ethylene glycol dimethacrylate (EGDMA), triethylene glycoldimethacrylate (TEGDMA) and urethane dimethacrylate (UEDMA).

The compositions of this invention contain at least a portion (1 wt %)of a solid thermoplastic elastomer thickener such as an acrylicionomer/acrylic block copolymer resin. Preferably about 35 wt. %, mostpreferably 35–70 wt. % of the total weight of the liquid monomer, liquidoligomer, liquid polymer or combination thereof of the thickener is usedin the composition. The solid thermoplastic elastomer thickenerparticipates in the cure. Suitable acrylic ionomers are based on theresin sold under the trade name Elvacite® 2051 by ICI. This highlyabsorbent solid acrylic resin is amorphous and thermoplastic andpreferably a linear and unbranched homopolymer. The acrylic resinpreferably has 1) a high molecular weight, preferably above 100,000,most preferably about 400,000 as determined by conventional gelpermeation chromatography (GPC) methods using conventional solvents foracrylic resins, such as methylene chloride; 2) a particle size of atleast one micron and preferably about 0.005 mm (5 microns) to 0.1 mm andmost preferably about 0.1 mm; and 3) essentially no active free-radicalpolymerization initiators. The solid acrylic resin preferably has aninherent viscosity of about 1.25 as tested in a Cannon-Fenske viscometerwith 0.25 grams in 50 ml of methylene chloride at 20° C.

The solid thermoplastic elastomer thickener such as the acrylicionomer/block copolymer resins absorb solvent, which in the compositionof the invention is the liquid monomer, oligomer or polymer. Thefunction of this solid thermoplastic elastomer thickener within themolding composition is to provide a delayed viscosity build, thuspermitting the prolonged mixing necessary to incorporate thoroughly wethigh volumes of filler and fiber into the molding composition.Absorption of the liquid monomer, oligomer or polymer is preferably notsubstantially complete until at least 2 hours after being mixed with thesolid acrylic resin. Most preferably, absorption of the liquid monomer,oligomer or polymer by the solid acrylic resin (viscosity build) issubstantially complete (about 90%) within 1 to 4 days from forming amixture thereof.

The delayed absorption of the liquid provides for a low viscosity whichis sufficiently low to enable bulk molding compounds, thick moldingcompounds and sheet molding compounds to be molded under thetemperatures and pressures of low pressure equipment.

The amount of acrylic ionomer or block copolymer (acrylics and vinylesters) within the compositions of this invention can vary widely,particularly when employed with other compatible resins. The amount ofacrylic ionomer (liquid and solid) preferably ranges from 35 to 95 wt. %of the liquid monomers, oligomers and/or polymers in the composition,more preferably from about 50–70 wt. % of these liquid components in thecomposition. Acrylic resins can form 100% of resin component of thecomposition except where vinyl ester resin is the “acrylic resin”.

The compositions of the present invention can include other resins whichwill either participate in the free-radical polymerization or remaininert during polymerization, functioning as organic fillers or otheradditive. Essentially any liquid or solid vinyl or diene containingmonomer, oligomer, polymer or copolymer which will participate infree-radical polymerization at ambient temperature can be used. Theseinclude polyesters and those derived from the monomers selected from thegroup consisting of vinyl ethers, acrylonitrile, styrene, propylene,vinyl acetate, vinyl alcohol, vinyl chloride, vinyldiene chloride,butadiene, isobutylene, isoprene, divinylbenzene and mixtures thereof.An example of an inert resin is polyethylene, which in particulate formcan function as an organic filler. However, it is preferable thatacrylic resins, i.e., those derived from the monomers of formula 1 andthe vinyl ester resins be used exclusively in the molding compositionsof this invention.

Embodiments of this invention include thermosetting molding compositionsand precursors thereto. The thermosetting molding compositions of thepresent invention include a free-radical polymerization initiator. Thisinitiator can be any conventional free-radical initiator. The initiatorpreferably has an activity which can be restrained (inhibited/retarded),preferably at ambient conditions and most preferably elevatedtemperatures. Free-radical initiators which initiate polymerization byexposure to either elevated temperatures above ambient temperatureand/or exposure to UV or visible light are well suited for providingmolding compositions with the requisite shelf stability of at least oneweek. Suitable temperature activated initiators include t-butylperoxybenzoate, sold under the trade name Trigonox® by Akzo ChemicalsInc., t-butyl hydro-peroxide and the peroxy ketals, also available fromAkzo Chemicals Inc. and the VASO catalysts such as VAZO-88® 1,1-azobi(cyclohexane carbonitrile) available from DuPont. Other suitableinitiators include ketone peroxides, alkyl peroxides, aryl peroxides,peroxy esters, perketals, peroxydicarbonates, alkylhydroperoxides,diacyl peroxides, VAZO compounds, photoinitiators and heat labilephotoinitiators.

Examples of ketone peroxides include methyl ethyl ketone peroxide,methyl isobutyl ketone peroxide, acetyl acetone peroxide andcyclohexanone peroxide.

Examples of alkyl peroxides and aryl peroxides include dicumyl peroxide,tert.butylcumyl peroxide, di-tert.amyl peroxide,1,3-di(2-tert.butylperoxy isopropyl)benzene, di-tert.butyl peroxide,2,5-dimethyl 2,5-di(tert.butylperoxy)hexane, 2,5-dimethyl2,5-di(tert.butylperoxy)hexane, dibenzoyl peroxide, tert.butyl3-isopropenylcumyl peroxide, 1,4-di(2-tert.butylperoxyisopropyl)benzene, 1,4-di(2-neodecanoyl peroxy isopropyl)benzene,di(1-hydroxycyclohexyl) peroxide, diisobutyryl peroxide, dioctananoylperoxide, didecanoyl peroxide and2,2-Bis(4,4-di(tert.butylperoxy-cyclohexyl)propane.

Examples of peroxyesters include tert-butyl peroxy-2-ethylhexanoate(Trigonox® 21), tert-amyl peroxy-2-ethylhexanoate (Trigonox® 121),tert-butyl peroxy-3,5,5-trimethylhexanoate (Trigonox® 42S), tert-butylperoxy-2-methylbenzoate (Trigonox® 97-C75), 2,5-dimethyl2,5-di(benzoylperoxy)hexane (AZTEC),2,5-dimethyl-2,5-di-(2-ethyl-hexanoylperoxy)hexane (Trigonox® 141),tert-butyl peroxy-isopropyl carbonate (Trigonox® BPIC), tert-butylperoxy-stearyl carbonate, tert.-butyl peroxyacetate, tert.-amylperoxyacetate, tert.-butyl peroxypivalate, tert.-amyl peroxypivalate,tert.-butyl peroxyneodecanoate, tert.-amyl peroxyneodecanoate,tert.-butyl peroxybenzoate, tert.-amyl peroxybenzoate (Trigonox® 127),tertiary-butyl peroxy 2-ethylhexyl carbonate, tertiary-amyl peroxy2-ethylhexyl carbonate, cumyl peroxyneodecanoate, cumylperoxyneoheptanoate, tertiary-butyl peroxyneoheptanoate, tertiary-butylperoxyisobutyrate, tertiary-butyl monoperoxy maleate and tert.-butylperoxydiethyl acetate.

Examples of perketals include 1,1-di(t-amylperoxy)cyclohexane (USP-90MD)2,2,-di(tert.butylperoxy)butane, n-butyl4,4-di(tert.butylperoxy)valerate ethyl 3,3-di(tert.butylperoxy)butyrate,3,3,6,6,9,9-hexamethyl 1,2,4,5-tetraoxa cyclononane,1,1-di-(tert-butylperoxy)-3,3,5-trimethylcyclohexane,1,1-di-(tert-butylperoxy)cyclohexane and di-tert.-butyldiperoxyazelate.

Examples of peroxy dicarbonates include di-(sec-butyl)peroxydicarbonate,di-(n-butyl)peroxydicarbonate, di-(2-ethylhexyl)peroxydicarbonatedi-(4-tert-butylcyclohexyl)peroxydicarbonate, dicyclohexylperoxydicarbonate, dimyristyl peroxydicarbonate and dicetylperoxydicarbonate.

Examples of alkylhydroperoxides include cumene hydroperoxide,1,4-di(2-hydroperoxy isopropyl)benzene, tert.amyl hydroperoxidetert.butyl hydroperoxide, 2,4,4-trimethylpentyl-2 hydroperoxide anddiisopropylbenzene monohydroperoxide

Examples of diacyl peroxides include acetyl cyclohexane sulphonylperoxide, di(2,4-dichlorobenzoyl)peroxide, di(3,5,5-trimethylhexanoyl)peroxide dilauroyl peroxide, disuccinic acid peroxide anddi(4-methylbenzoyl)peroxide.

Examples of VAZO compounds include2,2′-azobis(2,4-dimethylpentanenitrile),2,2′-azobis(2,4-dimethylvaleronitrile) (Vazo® 51),2,2′-azobis(2-methylpropanenitrile), 2,2′-azobis(isobutyronitrile)(Vazo® 64), 2,2′-azobis(methylbutanenitrile),2,2′-azobis(methylbutyronitrile) (Vazo® 67),1,1′-azobis(cyclohexanecarbonitrile) or 1,1′-azobis(cyanocyclohexane)(Vazo® 88).

Examples of photoinitiators include 2-butoxy-1,2-diphenylethanone,2,2-dimethoxy-1,2-diphenylethanone, a mixture ofoligo(2-hydroxy-2-methyl-1-(4-(1-methylvinyl)phenyl)propanone)+2-hydroxy-2-methyl-1-phenyl-1-propanone,oligo(2-hydroxy-2-methyl-1-(4-(1-methylvinyl)phenyl)propanone), amixture of2,4,6-trimethylbenzophenone+4-methylbenzophenone+oligo(2-hydroxy-2methyl-1-(4-(1-methylvinyl)phenyl)propanone), a mixture ofoligo(2-hydroxy-2-methyl-1-(4-(1-methylvinyl)phenyl)propanone)+2-hydroxy-2-methylphenyl 1-propanone,2,4,6-trimethylbenzoyldiphenylphosphine oxide+methylbenzylphenone, amixture of 2,4,6-trimethylbenzophenone+4-methylbenzophenone, a mixtureof 2-isopropylthioxanthone, ethyl 4-(dimethylamino)benzoate andmethyl-benzophenone, benzophenone and diaryl iodoniumhexafluoroantiomonate

Examples of miscellaneous initiators include triaryl sulfoniumhexafluorophosphate+propylene carbonate and triaryl sulfoniumhexafluoroantimonate+propylene carbonate.

To obtain stable mixtures, the initiator should be compatible with theacrylic resin and preferably, the acrylic resin is inhibited with themethyl ether of hydroquinone. Preferred curing initiators (andinhibitors) provide a formulation which remains stable for months,preferably at least from six months to one year, preferably in excess oftwo years. Such curing initiators are typically heat activated attemperatures well above ambient temperature and more typically above 75°C. An example of a preferred free-radical initiator which can beactivated at temperatures above 75° C., including temperatures above theglass transition temperature of polymethylmethacrylate acrylic resin(Tg=105° C.), is t-butyl peroxybenzoate. Activation temperatures in therange of 75° C. to 200° C. can be used with t-butylperoxybenzoate andare often preferred.

The curing initiator can be used in amounts analogous to the amountsused in conventional acrylic-based molding compositions, which typicallyrange from about 0.12 to 1.0 weight % of the molding composition, moretypically about 0.3 to 1.0 weight %.

An optional element of the compositions of the present invention isfiber reinforcement. These fibers are “long” fibers. The phrase “longfiber”, as used herein, is intended to refer to those fibers having anaspect ratio, which is the ratio of fiber length to fiber diameter(L/D), that is theoretically large enough to result in fiber fracturenear the midpoint when stressed. Long fibers comprised of conventionalreinforcement materials have an aspect ratio exceeding 5:1. The lowestvalue for the aspect ratio at which this first occurs is referred to asthe “critical aspect ratio.” The critical aspect ratio defines thecritical length at which a certain diameter fiber is considered “long”.Fibers of different materials such as, for example, aramid, glass,graphite, etc., have different critical aspect ratios. In addition,identical fibers embedded in different matrices such as, for example,matrices of acrylic, epoxy, and polyester resins, have differentcritical aspect ratios. Examples of critical aspect ratios and criticallengths for various reinforcements and matrices are shown in Table 1below.

TABLE 1 Fiber Matrix (l/d)₁ l_(c1) E-Glass Polypropylene 140 1.78 mmE-Glass Epoxy  34 0.43 E-Glass Polyester 100 1.27 Carbon Epoxy  47 0.33Carbon Polycarbonate 106 0.74 1 Engineering Materials Reference Book,2nd Ed., p. 77, Ed. Michael Bauccio, ASM International, 19941

The aspect ratio for fibers within a matrix comprised of a cured acrylicresin typically will be well above 5:1 for commercially available fiberreinforcements. Typically, the aspect ratio will be above 50:1 and it isoften above 150:1. Conventional reinforcement fibers of glass, aramid,graphite, etc. having a length as low as 0.25 mm can function as longfibers within the compositions of this invention once cured since thefibers are thin and their aspect ratios are high.

While the lower limit for the preferred lengths of the long fibers isabout 0.25 mm, the long fibers can be continuous, i.e. no measurablelimit, when the molding composition is in the form of a sheet. The longfibers utilized in the molding doughs provided by this invention do havean upper limit for the preferred fiber lengths of about 6.5 mm.Preferred lengths for continuous fibers are at least 1 inch. Suitabletypes of fibers are 1) inorganic crystals or polymers, such as fibrousglass, quartz fibers, silica fibers and fibrous ceramics, which includealumina-silica (refractory ceramic fiber), boron fibers, silicon carbidewhiskers or monofilament metal oxide fibers, includingalumina-boria-silica, alumina-chromia-silica, zirconia-silica, and thelike; 2) organic polymer fibers, such as fibrous carbon, fibrousgraphite, acetates, acrylics (including acrylonitriles), aliphaticpolyamides (e.g., nylons), aromatic polyamides, polyesters, flax,polyethylenes, polyurethanes (e.g., spandex), alpha-cellulose,cellulose, regenerated cellulose (e.g., rayon), jutes, sisals, vinylchlorides, e.g., vinyon, vinyldienes (e.g., saran) and thermoplasticfibers; 3) metal fibers, such as aluminum, boron, bronze, chromium,nickel, stainless steel, titanium and their alloys; and 4)“Whiskers”which are single, inorganic crystals.

The reinforcing fibers preferably comprise such materials as glass,metals, carbon, rayon, cellulose acetate, cellulose triacetate and thelike, Mylar® polyester, aramid/Kevlar®, Nomex® aramid fiber orpolyethylene fiber in continuous or discontinuous form. A preferredfiber is silanized chopped glass fiber. The preferred length of fiberreinforcement utilized with the acrylic-based doughs such as bulkmolding compounds (BMC), particularly Elvacite® 2051 bulk moldingcompounds, falls in the range of 0.25 to 6.5 mm. The length of fiberreinforcement utilized with vinyl ester BIS-GMA doughs preferably rangesfrom 0.1 to 6.5 mm. Fibers can be used in an amount of from 10 wt. % upto about 90 wt. % for sheet materials. In dough molding compositionssuch as BMC, levels of fiber reinforcement above 25 wt. % show littleadvantage, although higher levels such as 50 wt % can be easily used.The dough molding compositions (BMC) preferably have at least 10 wt. %long fiber. Sheet molding compounds (SMC) can use discontinuous orcontinuous reinforcing fibers, filaments, braided fabrics, knit fabrics,woven fabrics or loose laid fabrics.

A fiber composite is formed upon cure of the thermosetting moldingcompositions of the present invention. Where the thermosetting moldingcomposition provides a composite with discontinuous fibers, the stressalong the fiber is not uniform. There are portions along each fiber endwhere the tensile stresses are less than that of a fiber that iscontinuous in length. This region is often called the fiber ineffectivelength. The tensile stress along the fiber length increases to a maximumalong the middle portion of the fiber. If the fiber is sufficiently long(critical length) so that the ratio of the length to diameter, or aspectratio, equals or exceeds the critical aspect ratio, the mid-fiber stresswill be equal to that of a continuous filament.

The critical aspect ratio which would result in fiber fracture at itsmid-point can be expressed as (l/d)_(c)=S_(f)/2Y. Where (l/d)_(c)=thecritical aspect ratio, l=length of the fiber and w=width of the fibers,S_(f) is the tensile stress of the fiber and Y is the yield strength ofthe matrix in shear or the fiber-matrix interfacial shear strength,whichever value is lower.

If the fiber is shorter than the critical length, the stressed fiberwill de-bond from the matrix and the composite will have low strength.When the length is greater than the critical length, the stressedcomposite will not de-bond the fibers and will exhibit high strength.

The rule of mixtures for discontinuous fiber composites may be expressedas S_(c)=V_(f)·S_(f)(l−l_(c)/2l)+V_(m)S_(m) where S_(c) is the tensilestrength of the composite, S_(m) is tensile strength of the matrix, l isthe actual length of the fiber, l_(c) is the critical length of thefiber, V_(f) is the volume fraction of the fiber and V_(m) is the volumefraction of the matrix. For the composite to have a higher strength thanits matrix, a minimum V_(f) must be exceeded. This value may be 0.1 orgreater for the plastic matrix composites. Because of high stressconcentrations at the discontinuities that occur at the fiber ends,tensile strength of a discontinuous fiber composite will be from about55% to 86% of the fiber tensile strength and the modulus can approach90% to 95% of the corresponding continuous fiber composite.

The molding compositions of this invention can contain conventionaladditives where desired to obtain a particular additive effect either inprocessing or in the finished product. These include mechanical propertymodifiers, processing aids, surface property modifiers, physicalproperty modifiers, and electrical property modifiers. Specificadditives include anti-blocking agents, anti-caking agents, anti-foamingagents, antioxidants, anti-slip agents, anti-static agents, blowingagent, coupling agents, compatibilizers, dispersing aids, flattingagents, inhibitors, catalysts, accelerators/promoters, heat stabilizers,light stabilizers, wetting agents, plasticizers, extenders,thixotropics, flame, fire and smoke retarders, internal mold releases,lubricants, impact modifiers, tougheners, coloring/dyes/pigments,odorants and deodorants, low profile or low shrink additives, lowpressure additives, clarifying agents, opacifiers, thickeners, viscositycontrol agents, permeability modifiers, biodegrading agents, flameretardants, foaming agents, blowing agents, solvents and waxes can beused. Conventional colorants can be used, such as dyes or pigments whennecessary. In dental appliances, titanium dioxide and cadmium (peachcolored) pigments are often used. The amount of colorant typicallyranges from about 0.1–1.0 wt. % of the molding composition. Othersuitable additives are dispersing agents, typically used in an amount of1 to 8 wt. % of the molding compositions. An example of suitabledispersing agent is fumed silica sold under the trade name Cab-O-Sil®.Other additives include surfactants and mold release agents. Suitablemold release agents are stearate/sterol alcohol and suitable surfactantsare di-octylsulfosuccinate (sodium salt). The mold release agents aretypically used in an amount of from 0.2–1.0 wt. % of the moldingcomposition and the surfactants are used in the amount of 0.01 to 0.5wt. % of the molding composition.

It may be desirable to add fillers, either inorganic or organic, with orwithout fiber reinforcement to reduce shrinkage and distortion andimprove the physical properties of the resulting composite. Preferredexamples of inorganic fillers include silicate glass, fused silica,quartz and silinated glass ballotini. Others include calcium carbonatesof various forms and origins, silica of various forms and origins,silicates, silicon dioxides of various forms and origins, clays ofvarious forms and origins, calcium sulfates, micas, talcs, wood invarious forms, glass (milled, platelets, spheres, micro-balloons)plastics (milled, platelets, spheres, micro-balloons), recycled polymercomposite particles, metals in various forms, metallic oxides orhydroxides, metal hydrides or metal hydrates, carbon particles orgranules, alumina (tabular), aluminum powder, aramid, bronze, carbonblack, carbon fiber, cellulose, alpha cellulose, coal (powdered),cotton, fibrous glass, graphite, jute, molybdenum disulfide, nylon,orlon, rayon, silica (amorphous), sisal fibers, fluorocarbons, woodflour, kaolin, flax, zirconia and Feldspar. Although the moreconventional metal oxide fillers such as magnesium oxide and calciumoxide do not inhibit the immediate physical properties of the resultingproduct and are suitable for the molding compositions of this invention,they do cause the molding compositions to thicken over time andtherefore, molding compositions essentially free of these metal oxidesthickeners are preferred. Metal oxide thickeners form ionic polymernetworks with resin carboxyl groups requiring high pressure to breakthese bonds.

As to the organic fillers, the solid thermoplastic elastomer thickenerparticipates in the reaction unlike conventional fillers, an examplebeing Elvacite® 2051 (ICI), which is a thermoplastic polymethylmethacrylate free of benzoyl peroxide catalytic initiator. The organicfillers which do not react are typically used in an amount from about 0to 30 wt. %, but compositions of this invention with preferred levels oforganic fillers typically range from 0 to 20 wt. %, based on the totalcompound.

Compositions of this invention can be prepared using conventional mixingequipment such as a high shear blender. The components of the moldingcomposition are preferably first combined into two separate portions, aliquid mixture portion and solid mixture portion. The liquid mixtureincludes the liquid acrylic monomer, oligomer or polymer (vinyl esterresin, or polyester resin) optionally surfactant and catalyst. The dryingredients are mixed thoroughly in a high shear blender and typicallyinclude the solid thermoplastic elastomer thickener (such as the acrylicionomer/block copolymer) colorants, dispersing agents. Preferably, thereinforcing fibers are not blended into the solid mixture. Followingpreparation of the solid and liquid mixture portions, the two portionsare combined in a low shear mixer for about five minutes, followingwhich the reinforcing fibers are slowly added over an extended period.The fiber reinforcement is mixed so that there is no agglomeration offibers and a uniform distribution is obtained by wetting these fibers.Once the fibers have been distributed throughout the liquid component,the mixture is allowed to stand (mature) for about two to five days withoccasional stirring. This technique provides a bulk-molding compound(BMC) consistent with the present invention. In forming sheet moldingcompounds (SMC), a mixture of liquid and solid components or a singlecomponent formulation are applied to a continuous fiber network ofeither knit, woven, sewn or braided fabrics or loose-lay filaments.

With the appropriate curing initiator blended therein, the thermosettingmolding composition can be hardened by the application of heat orexposure to UV or visible light. The methods of this invention aresuitable for preparing compositions with no polymerization initiator orwith polymerization initiators that are active or inactive at ambienttemperature. The vinyl ester resin blends are well suited for use withcuring initiators that are activated by exposure to bright light. Of theheat-cured resins, those which are activated at temperatures above 75°C. are preferred. Such temperatures are typically above the glasstransition temperature of the acrylic resin which forms the matrix. Thethermosetting molding compositions can be conveniently cured attemperatures of from 75° C. to 200° C. in an oil bath.

The compositions of this invention are well suited for producingdentures, inlays, crowns, bridgework, orthodontic devices, etc. However,these molding compositions are not confined to uses within the fields ofdentistry, orthopedics and podiatry. These compositions can be used inindustrial applications such as model making and the production ofutensils, automotive parts, bathroom fixtures and wherever enhancedphysical properties must be combined with weatherability and ease ofprocessing.

Without further elaboration, it is believed that one skilled in the artcan, using the preceding description, utilize the present invention toits fullest extent. The following preferred specific embodiments are,therefore, to be construed as merely illustrative, and not limitative ofthe remainder of the disclosure in any way whatsoever.

In the foregoing and in the following examples, all temperatures are setforth in degrees Celsius; and, unless otherwise indicated, all parts andpercentages are by weight. In addition, unless otherwise indicated, allresin formulations are inhibited with trace amounts of eitherhydroquinone or methylethyl hydroquinone.

The disclosure of all patents and publications mentioned above and beloware hereby incorporated by reference.

Protocol A

Stable, reinforced, thermoset, molding doughs of this invention areprepared according to the following protocol:

Phase 1: combine by TOTAL weight percent and mix separately as parts Aand B:

Part A—The Liquid:

-   -   46 parts methylmethacrylate monomer;    -   8 parts ethylmethacrylate monomer;    -   4.5 parts ethyleneglycol dimethacrylate (cross-linker);    -   0.2 parts t-butyl peroxybenzoate (initiator);    -   0.1 parts dioctylsulfosuccinate, sodium salt (surfactant) and    -   A trace of methylethylhydroquinone (inhibitor).        Mix liquids thoroughly in a high shear blender, e.g. Lightin®        shear blender for 5 minutes.

Part B—The Powder:

-   -   1.0–8.% dispersing agent (Silica);    -   Colorants: TiO₂, dyes and/or pigments;    -   33 parts acrylic ionomer thickener formed from Elvacite® 2051        (ICI) polymethyl methacrylate;    -   5 parts Aramid PULP, no. 543; and    -   0.2 parts (peach) pigment.        Mix powders very thoroughly in a high shear blender for 5        minutes. Phase 2: Combine liquid and powder by adding Part B,        powder, to Part A, liquid, in a low shear mixer, e.g., Ross,        Double Planetary machine, and mix for 45 minutes. Transfer to a        sealed container and allow to stand (mature) for 1–4 days at        70° F. Occasional turning or stirring may be needed during        maturation, depending on the formula, to incorporate free,        liquid monomer.

The end product is a thick, pliable putty with a minimal tack.

Protocol B:

Stable, reinforced, thermoset, molding doughs of the present inventionare prepared as follows:

Phase 1: Combine by weight and mix, separately, parts A and B:

Part A—The Liquid: A terpolymer resin mixture of:

-   -   70 grams methyl methacrylate resin;    -   20 grams ethyl methacrylate resin;    -   10 grams Bis-GMA vinyl ester resin, e.g., Nupol® Bis-GMA vinyl        ester resin 046–4005;    -   0.25 grams catalyst (t-butyl peroxybenzoate, or t-butyl        hydro-peroxide, peroxy-ketals or VAZO® catalyst);    -   0.14 grams di-octylsulfosuccinate (sodium salt), a surfactant.

Part B—The Powder: Mix very thoroughly in a high shear blender:

-   -   5.0 grams silica dispersing agent;    -   0.4 grams Colorants: “Cadmium” pigment;    -   40.0 grams methylmethacrylate ionomer thickener prepared from        Elvacite® 2051 methylmethacrylate polymer (ICI), which is free        from benzoyl peroxide catalytic initiator;    -   6.0 grams fibrillated polyethylene, Short Stuff® polyethylene,        for mold lubrication, reduction of shrinkage and distortion, and        to physically stabilize the suspension of the various powders in        the mixture;    -   2.0 grams Calcium silicate (optional) to facilitate processing;    -   20.0 grams silinated, glass ballotini.

Part C,

-   -   25.0 grams Reinforcing fibers: glass, metals, carbon, nylon,        aramid fiber (KEVLAR®), especially in its fibrillated forms,        e.g., DuPont's 540–543 aramid fiber (KEVLAR®) pulp, or, Nomex®        aramid fiber.

Phase 2:

1) Place 75 grams of Part A—“The Liquid” in a low shear mixer, add PartB—“The Powder” and mix slowly and thoroughly for 5 minutes.

2) Slowly add Part C, 25.0 grams of reinforcing fibers, and continue tomix for 15 minutes.

Cover the mix in a sealed container and allow to stand (mature) for 2–4days. Occasional stirring or turning may be needed, depending on theformula, to incorporate free liquid resin.

The end product is a thick, pliable putty with a minimal tack.

A typical bulk molding formulation is as follows:

wt. % solid acrylic ionomer 26 liquid monomer 2.5 calcium carbonate 50zinc stearate (mold release) 1 t-butyl peroxide benzoate .5 glass fibers(¼ in) 20

Sheet molding compound is composed of basically four principleingredients: the thermnosetting components (liquid monomer, oligomer orpolymer, and solid acrylic resin), fiber reinforcement, optionallyadditives and optionally fillers. It is feasible to use various types ofspecific ingredients for each of the four principle ingredients suchthat an almost indefinite number of formulations are possible.

The sheets are stored to age in a controlled environment. The maturationperiod (normally 2 to 5 days) is, in effect, the time needed for thepaste viscosity to reach a level sufficient for molding. The pasteviscosity at the time of compound is typically below 40,000 cps(mPas·s), whereas at the time of molding, the viscosity is preferably20×10⁶ to 30×10⁶ cps.

SMC Formulation with Thermoplastic Resin SMC Paste Part by Wt. RangeSolid acrylic resin 60 15–25 Liquid monomer 100 20–25 Thermoplasticresin 40  5–12 Calcium carbonate 150 20–40 (3–5 μm particle size)t-butyl peroxybenzoate 1.5 Zinc stearate (mold release) 4.0 Fiberglass - Chopped 125 20–40 (1 inch)

EXAMPLES 1–4

Examples 1–4 describe bulk molding compounds of this invention preparedin accordance with Protocol A. The components of these molding compoundsare shown in Table 2 below wherein all % are in wt. %:

TABLE 2 Example No. 1 2 3 4 Resin, Liquid Methyl methacrylate 61.00%30.50% Ethyl methacrylate 61.00% 30.50% Other Acrylic Resins or 63.00%Copolymers Curing Agent(s) t-butyl peroxybenzoate  0.30%  0.30%  0.30% 0.30% Thickener Cab-O-Sil, fumed silica  2.00%  2.00%  2.00%  2.00%Acrylic ionomer powder* 36.70% 36.70% 36.70% 34.70% *All thickeningand/or polymer powder is benzoyl peroxide free. Example: ICI's,Elvacite ® 2051, or, Elvacite ® 2697 modified by the addition of a salt.

EXAMPLES 5–8

Examples 5–8 describe bulk-molding compounds of this invention preparedin accordance with protocol A. The components of the molding compoundsare shown in Table 3 below.

TABLE 3 Example No.: 5 6 7 8 Resin, Liquid Methyl methacrylate 43.11%35.00% 40.00% Ethyl methacrylate  8.11%  8.10% Other Acrylic Resins or52.05% Copolymers Reinforcement Glass Fiber 15.00% 15.00% Others**15.00% 15.00% Mineral Filler Glass/Quartz 20.00% 20.00%  9.00% Feldspar 5.00% Organic Filler 13.00% (Example: Powdered polyethylenes) CouplingAgent Silane  2.00%  2.00%  2.00%  2.00% Curing Agent(s) t-butylperoxybenzoate  0.25%  0.25%  0.30%  0.30% Thickener Acrylic PolymerPowder 17.34% 17.34% 15.35% 15.35% Silica  2.00%  2.00%  2.00%  2.00%Low Profile Additive: Polyethylene Powder or  3.00% Pulp **Includesthose selected from metal fibers and flakes, phosphate fiber,Wallostonite, Dawsonite, Micro Fiber glass, processed mineral fiber,TISMO (old Fibex), magnesium oxysulfate fiber (MOS)

Without further elaboration, it is believed that one skilled in the artcan, using the preceding description, utilize the present invention toits fullest extent. The following preferred specific embodiments are,therefore, to be construed as merely illustrative, and not limitative ofthe remainder of the disclosure in any way whatsoever.

1. A method of preparing a shelf-stable composition which comprises: a)mixing a solid thermoplastic elastomer thickener which is athermoplastic ionomer that has secondary bonding with one or morereactive liquid monomers, liquid oligomers, liquid polymers or acombination thereof which polymerizes in the presence of an activatedfree-radical polymerization initiator, wherein said secondary bondingcomprises ionic bonds wherein said solid thermoplastic elastomerthickener is free of active free-radical polymerization initiators,absorbs said reactive liquid monomers, liquid oligomers, liquid polymersor combination thereof, and reacts with said reactive liquid monomers,liquid oligomers, liquid polymers or combination thereof, in thepresence of an activated free-radical polymerization initiator; and b)aging the mixture of solid thermoplastic elastomer thickener, andreactive liquid monomers, liquid oligomers, liquid polymers orcombination thereof, for at least 24 hours to allow absorption of thereactive liquid monomer, liquid oligomer, liquid polymer or combinationthereof by the solid thermoplastic elastomer thickener.
 2. A method asin claim 1, wherein long fiber reinforcement is additionally mixed withsaid solid thermoplastic elastomer thickener, wherein said long fiberreinforcement is insoluble in said thermoplastic elastomer thickener,has an aspect ratio, L/D, greater than 5:1 and has a length at leastabout 0.25 mm.
 3. The method as in claim 2 comprising the additionalstep of mixing a free-radical polymerization initiator with said mixtureof solid thermoplastic elastomer thickener, reactive liquid monomers,liquid oligomers, liquid polymers or combination thereof and long fiberreinforcement wherein the free-radical polymerization initiator isinactive at ambient temperature or its activity can be restrained underambient conditions.
 4. A method as in claim 1 wherein the thermoplasticionomer comprises a polymer backbone with up to 20 mol % of carboxylategroups, sulfonate groups, phosphate groups, pyridine groups and aminogroups positioned on the polymer backbone.
 5. A method as in claim 4wherein the polymer backbone is derived from free-radical polymerizationof vinyl unsaturation.
 6. A method as in claim 5 wherein the polymerbackbone is derived from acrylate monomers, methacrylate monomers,acrylic monomers, methacrylic monomers, urethane monomers, and vinylalcohol monomers.
 7. A method as in claim 1 wherein the solidthermoplastic elastomer thickener is an acrylic polymer combined with aninorganic salt having Na⁺, Li⁺, Mg⁺⁺ or Zn⁺⁺ ions.
 8. A method as inclaim 7 wherein the acrylic polymer is polymethylmethacrylate.
 9. Amethod as in claim 7 comprising the additional steps of heating a solidacrylic polymer to inactivate any free radical polymerization initiatorstherein and adding an inorganic salt to the heated acrylic polymer toform an ionomer.
 10. A method as in claim 1, wherein said solidthermoplastic elastomer is a solid acrylic ionomer.
 11. A method as inclaim 10 which comprises a solid acrylic ionomer resin selected from thegroup consisting of linear homopolymers or copolymers of acrylate ormethacrylate monomers.
 12. A method as in claim 1, wherein the reactiveliquid monomer has vinyl unsaturation and is selected form the groupconsisting of acrylic acid monomers, methacrylic acid monomers, acrylatemonomers, methacrylate monomers, vinyl ether monomers, acrylonitrilemonomers, propylene monomers, vinyl acetate monomers, vinyl alcoholmonomers, vinyl chloride monomers, vinylidine chloride monomers,butadiene monomers, isobutadiene monomers, isoprene monomers, divinylbenzene and mixtures thereof and the reactive liquid oligomer isselected from acrylic oligomers, methacrylic oligomers, styreneoligomers, vinyl ester oligomers and polyester oligomers.
 13. A methodas in claim 1, wherein said fiber reinforcement is selected from thegroup consisting of glass fibers, carbon fibers, metal fibers, rayonfibers, aramid fibers and polyolefin fibers.
 14. A method of preparing ashelf-stable composition which comprises: a) mixing a solidthermoplastic elastomer thickener which has secondary bonding with oneor more reactive liquid monomers, liquid oligomers, liquid polymers or acombination thereof which polymerizes in the presence of an activatedfree-radical polymerization initiator, wherein said secondary bondingcomprises ionic bonding, hydrogen bonding, Van Der Waals forces,physical chain entanglements and crystal lattice interactions, whereinsaid solid thermoplastic elastomer thickener is free of activefree-radical polymerization initiators, absorbs said reactive liquidmonomers, liquid oligomers, liquid polymers or combination thereof, andreacts with said reactive liquid monomers, liquid oligomers, liquidpolymers or combination thereof, in the presence of an activatedfree-radical polymerization initiator; and b) aging the mixture of solidthermoplastic elastomer thickener, and reactive liquid monomers, liquidoligomers, liquid polymers or combination thereof, for at least 24 hoursto allow absorption of the reactive liquid monomer, liquid oligomer,liquid polymer or combination thereof by the solid thermoplasticelastomer thickener and comprising the additional step of mixing alkaliearth metal filler with the solid thermoplastic elastomer thickener andone or more reactive liquid monomers, liquid oligomers, liquid pigmentsor combination thereof.
 15. A method as in claim 2, wherein the longfiber reinforcement comprises 15 wt. % to 50 wt. % of the totalcomposition.
 16. A method as in claim 10, wherein the solid acrylicionomer resin absorbs at least 90% of the reactive liquid monomers,liquid oligomers, liquid polymers or combination thereof, andsubstantial viscosity build is delayed for at least two hours after thesolid acrylic ionomer resin is mixed with the reactive liquid monomer,liquid oligomer, liquid polymer or combination thereof.
 17. A method asin claim 11, wherein the absorption of at least 90% of the liquidmonomers, liquid oligomers, liquid polymers or combination thereof, bythe solid acrylic ionomer resin is complete in 1 to 4 days from mixingthe solid acrylic ionomer resin with the liquid monomer, liquid,oligomer, liquid polymer or combination thereof.
 18. A composition whichcomprises: a) a reactive liquid monomer, liquid oligomer, liquid polymeror combination thereof with vinyl unsaturation, which polymerizes in thepresence of an activated free-radical polymerization initiator; b) atleast 1 wt. %, based on the total weight of the reactive liquid monomer,liquid oligomer, liquid polymer or combination thereof in thecomposition, of a solid thermoplastic elastomer thickener which i) issoluble in said reactive liquid monomer, liquid oligomer, liquid polymeror combination thereof, and ii) reacts with the reactive liquid monomer,liquid oligomer, liquid polymer or combination thereof containing vinylunsaturation in the presence of an activated free-radical polymerizationinitiator; iii) is free of active free-radical polymerizationinitiators, iv) has at least a portion of said reactive liquid monomer,liquid oligomer, liquid polymer or combination thereof absorbed therein;and v) comprises a solid thermoplastic ionomer with secondary bondingcomprising ionic bonds, c) a free-radical polymerization initiator, theactivity of which can be restrained under ambient conditions or isinactive at ambient temperature so as to provide a shelf life of atleast one month at ambient temperature.
 19. A thermosetting moldingcomposition as in claim 18, wherein the free-radical polymerizationinitiator is activated by exposure to ultraviolet light, visible lightor a temperature above 75° C.
 20. A composition as in claim 18, whereinthe particles of solid thermoplastic elastomer thickener have an averageparticle size in the range of 0.005 mm (5 microns) to 0.5 mm.
 21. Acomposition as in claim 18, wherein the amount of solid thermoplasticelastomer thickener within the molding composition is at least 35 wt %,based on the total weight of reactive liquid monomer, liquid oligomer,liquid polymer or combination thereof in said composition.
 22. Acomposition of claim 18 wherein the solid thermoplastic elastomerthickener is an acrylic ionomer.
 23. A composition as in claim 22wherein the acrylic ionomer is a linear homopolymer or copolymer ofacrylate or methacrylate monomers.
 24. A composition as in claim 23,wherein the reactive liquid monomer has vinyl unsaturation and isselected from the group consisting of acrylic acid monomers, methacrylicacid monomers, acrylate monomers, methacrylate monomers, vinyl ethermonomers, acrylonitrile monomers, propylene monomers, vinyl acetatemonomers, vinyl alcohol monomers, vinyl chloride monomers, styrenemonomers vinylidine chloride monomers, butadiene monomers, isobutadienemonomers, isoprene monomers, divinyl benzene and mixtures thereof, andthe reactive liquid oligomer has vinyl unsaturation and is selected fromthe group consisting of acrylic oligomers, methacrylic oligomers,styrene oligomers, vinyl ester oligomers, and polyester oligomers.
 25. Acomposition as in claim 18 in the form of a bulk molding compound whichadditionally comprises at least 10 wt % of long fiber reinforcementwhich is insoluble in said solid thermoplastic elastomer thickener andhas an aspect ratio (L/D) greater than 5:1 and an average length of atleast 0.25 mm.
 26. A composition as in claim 18 in the form of a sheetmolding compound which additionally comprises at least 25 wt % of longfiber reinforcement which is insoluble in said solid thermoplasticelastomer thickener and has a length greater than 0.25 mm.
 27. Acomposition as in claim 25 wherein said fiber reinforcement is selectedfrom the group consisting of glass fibers, carbon fibers, metal fibers,rayon fibers, aramid fibers, and polyolefin fibers.
 28. A composition asin claim 26, wherein said fiber reinforcement is selected from the groupconsisting of glass fibers, carbon fibers, metal fibers, rayon fibers,aramid fibers, and polyolefin fibers.
 29. A composition as in claim 18,wherein at least 90% of said reactive liquid monomer, oligomer, polymeror combination thereof, is absorbed by said solid thermoplasticelastomer thickener.
 30. A composition which comprises: a) a liquidmonomer, liquid oligomer, liquid polymer or combination thereof whichpolymerizes in the presence of an activated free-radical polymerizationinitiator; b) a solid acrylic ionomer resin which (i) is soluble in saidliquid monomer, liquid oligomer, liquid polymer or combination thereofcontaining vinyl unsaturation, (ii) has an average particle size in therange of 0.005 mm to 0.5 mm, (iii) has at least a portion of said liquidmonomer, liquid oligomer, liquid polymer or combination thereofcontaining vinyl unsaturation absorbed therein, (iv) reacts with saidliquid monomer, oligomer, polymer or combination thereof, and (v) isfree of free-radical polymerization initiators; c) 0.5 wt. % or more,based on the total weight of the composition, of long fiberreinforcement having an aspect ratio (L/D) greater than 5:1 and anaverage length of at least 0.25 mm, wherein said composition is shelfstable for at least one month.
 31. A composition as in claim 30 which isfree of alkali earth metal oxide fillers.
 32. A composition whichcomprises: a) a liquid monomer with vinyl unsaturation which cures to athermoset resin in the presence of an activated free-radicalpolymerization initiator; b) at least 35 wt. %, based on the totalweight of the liquid monomer in the composition, of a solidthermoplastic acrylic ionomer which is essentially free of activefree-radical polymerization initiators; c) a free-radical polymerizationinitiator.
 33. A composition as in claim 32 which additionally comprisesat least 10 wt % of long fiber reinforcement having an aspect ratio(L/D) greater than 5:1.
 34. A composition as in claim 30 whichadditionally comprises a solid resin, other than said solidthermoplastic elastomer thickener, which polymerizes in the presence ofan activated free-radical polymerization initiator.
 35. A composition asin claim 30 for the preparation of dental appliances, which comprises acuring catalyst and long fiber reinforcement having an aspect ratio(L/D) greater than 5:1, and which has a shelf life of at least 1 week.36. A composition as in claim 35, which has a shelf life of at least 1year.
 37. A composition as in claim 35, wherein said curing catalyst isheat activated at temperatures above 75° C. and said composition remainsstable at ambient temperature.
 38. A composition as in claim 37, whichis completely cured when heated to a temperature in the range of 75° C.to 200° C.
 39. A composition as in claim 38, which comprises a solidacrylic ionomer resin selected from the group consisting of monomers,oligomers and polymers of methyl methacrylate, ethyl methacrylate, vinylester resin and combinations thereof mixed with an inorganic salt andthe amount of said solid acrylic ionomer resin is at least 10 wt. %,based on the weight of the total composition.
 40. A composition as inclaim 35, which additionally contains a liquid or solid vinyl or dienemonomer, oligomer, polymer or copolymer derived from monomers selectedfrom the group consisting of vinyl ethers, acrylonitrile, styrene,propylene, vinyl acetate, vinyl alcohol, vinyl chloride, vinyldienechloride, butadiene, isobutylene, isoprene, divinylbenzene and mixturesthereof.
 41. A composition for the preparation of dental appliances,which comprises a solid acrylic ionomer resin, a heat-activated curingcatalyst which is stable at ambient temperature and 2 to 90 wt. %, basedon the weight of the total composition, of long fiber reinforcementhaving an aspect ratio (L/D) greater than 5:1 and an average length offrom 0.25 mm to 6.5 mm, which has a shelf life of at least 1 week and iscured when heated to a temperature of from 75° C. to 200° C.
 42. Acomposition as in claim 41, wherein the curing catalyst is selected fromthe group consisting of t-butyl perbenzoate, t-butyl hydro-peroxide,peroxy ketals and Vazo 88 and said composition is essentially free ofbenzoyl peroxide catalyst.
 43. A composition as in claim 41, which isfree of alkaline earth metal oxide particulate fillers as chemicalthickeners.